US8759541B2 - Chiral acyclic diaminocarbene ligands, precursors therefore and their use in organic synthesis reactions - Google Patents

Chiral acyclic diaminocarbene ligands, precursors therefore and their use in organic synthesis reactions Download PDF

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US8759541B2
US8759541B2 US13/003,039 US200913003039A US8759541B2 US 8759541 B2 US8759541 B2 US 8759541B2 US 200913003039 A US200913003039 A US 200913003039A US 8759541 B2 US8759541 B2 US 8759541B2
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Avinash N. Thadani
Rukundo Ntaganda
Mira M. Beshai
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
    • C07D207/09—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Definitions

  • the present disclosure is in the field of metal catalysts for organic synthesis reactions, in particular to metal catalysts comprising a chiral acyclic diamino carbene ligand.
  • TM catalysis has revolutionized organic synthesis. 2
  • the near constant improvement in the field of TM catalysis is undoubtedly due in large part to the introduction of new and improved ligands, which allows for desired transformations to be carried out in a more efficient manner (i.e. milder conditions, lower catalyst loadings, higher yields and higher enantioselectivities when applicable).
  • NHC N-heterocyclic carbenes
  • ADC acyclic diamino carbenes
  • a new array of chiral ADC ligands that have been employed in enantioselective catalysis has been developed.
  • a variety of symmetric and non-symmetric chiral acyclic formamidium salts have been prepared as precursors to their corresponding diamino carbenes.
  • Various metal catalysts having these chiral ADC's as ligands have also been prepared and used in metal-catalyzed organic synthesis transformations.
  • the present disclosure includes a metal catalyst of the formula I: M[ADC][X] n (I) wherein M is a metal; ADC is a chiral acyclic carbene of the formula II:
  • R 1 , R 2 , R 3 and R 4 are independently selected from C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, C 3-10 cycloalkyl, heteroaryl and aryl, each group being optionally substituted, or R 1 and R 2 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic or polycyclic, saturated or unsaturated ring system that contains 3 to 30 carbon atoms, of which one or more of the carbon atoms is optionally replaced with a heteromoiety selected from O, S, NH and NC 1-6 alkyl, and/or R 3 and R 4 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic or polycyclic, saturated or unsaturated ring system that contains 3 to 30 carbon atoms, of which one or more of the carbon atoms is optionally replaced with a heteromoiety selected from O, S, NH and NC 1-6 alkyl, the
  • R 1 , R 2 , R 3 , R 4 , the ring system formed by R 1 and R 2 and the ring system formed by R 3 and R 4 , or a substituent thereon, comprises at least one chiral center;
  • X is a neutral or an anionic ligand
  • n is an integer representing the number of ligands, X, to fulfill the valency requirements of N, and when x is greater than 1, each X may be the same or different.
  • the present disclosure includes a chiral formamidium salt of the formula III:
  • R 1 , R 2 , R 3 and R 4 are independently selected from C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, C 3-10 cycloalkyl, heteroaryl and aryl, each group being optionally substituted, or R 1 and R 2 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic or polycyclic, saturated or unsaturated ring system that contains 3 to 30 carbon atoms, of which one or more of the carbon atoms is optionally replaced with a heteromoiety selected from O, S, NH and NC 1-6 alkyl, and/or R 3 and R 4 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic or polycyclic, saturated or unsaturated ring system that contains 3 to 30 carbon atoms, of which one or more of the carbon atoms is optionally replaced with a heteromoiety selected from O, S, NH and NC 1-6 alkyl, and
  • the present disclosure also includes a method of performing metal-catalyzed organic synthesis reactions comprising contacting substrates for the organic synthesis reaction with a metal catalyst of the formula I as defined above under conditions for performing the organic synthesis reaction, and optionally isolating one or more products from the organic synthesis reaction.
  • the organic synthesis reaction is any reaction that benefits from the presence or use of a metal catalyst, for example, but not limited to, hydrosilations, hydrogenations, conjugate additions and cross-couplings.
  • the organic synthesis transformation is an asymmetric or chiral synthesis reaction (i.e. provides one enantiomer in excess of the other).
  • FIG. 1 is an X-ray crystal structure of (2R,5R)-1-(((2R,5R)-2,5-diphenylpyrrolidin-1-yl)methylene)-2,5-diphenylpyrrolidinium iodide (compound IIIj; Y ⁇ I ⁇ ).
  • C 1-n alkyl as used herein means straight and/or branched chain, saturated alkyl groups containing from one to “n” carbon atoms and includes (depending on the identity of n) methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, 2,2-dimethylbutyl, n-pentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-hexyl and the like, where the variable n is an integer representing the largest number of carbon atoms in the alkyl group.
  • C 1-n alkenyl as used herein means straight and/or branched chain, unsaturated alkyl groups containing from one to n carbon atoms and one to three double bonds, and includes (depending on the identity of n) vinyl, allyl, 2-methylprop-1-enyl, but-1-enyl, but-2-enyl, but-3-enyl, 2-methylbut-1-enyl, 2-methyl-pent-1-enyl, 4-methylpent-1-enyl, 4-methylpent-2-enyl, 2-methylpent-2-enyl, 4-methylpenta-1,3-dienyl, hexen-1-yl and the like, where the variable n is an integer representing the largest number of carbon atoms in the alkenyl group.
  • C 1-n alkynyl as used herein means straight and/or branched chain, unsaturated alkyl groups containing from one to n carbon atoms and one to three bonds, and includes (depending on the identity of n) propargyl, 2-methylprop-1-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, 2-methylbut-1-ynyl, 2-methylpent-1-ynyl, 4-methylpent-1-ynyl, 4-methylpent-2-ynyl, 2-methylpent-2-ynyl, 4-methylpenta-1,3-diynyl, hexyn-1-yl and the like, where the variable n is an integer representing the largest number of carbon atoms in the alkynyl group.
  • C 3-n cycloalkyl as used herein means a monocyclic, bicyclic or tricyclic saturated carbocylic group containing from three to n carbon atoms and includes (depending on the identity of n) cyclopropyl, cyclobutyl, cyclopentyl, cyclodecyl and the like, where the variable n is an integer representing the largest number of carbon atoms in the cycloalkyl group.
  • aryl as used herein means a monocyclic, bicyclic or tricyclic aromatic ring system containing from 6 to 14 carbon atoms and at least one aromatic ring and includes phenyl, naphthyl, anthracenyl, 1,2-dihydronaphthyl, 1,2,3,4-tetrahydronaphthyl, fluorenyl, indanyl, indenyl and the like.
  • heteroaryl as used herein means a monocyclic, bicyclic or tricyclic ring system containing one or two aromatic rings and from 5 to 14 atoms of which, unless otherwise specified, one, two, three, four or five are heteroatoms independently selected from N, NH, N(C 1-6 alkyl), O and S and includes thienyl, furyl, pyrrolyl, pyrididyl, indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like.
  • halo as used herein means halogen and includes chloro, fluoro, bromo and iodo.
  • ring system refers to a carbon-containing ring system, that includes monocycles, fused bicyclic and polycyclic rings and bridged rings. Where specified, the carbons in the rings may be substituted or replaced with heteroatoms.
  • the present disclosure includes a metal catalyst of the formula I: M[ADC][X] n (I) wherein M is a metal; ADC is a chiral acyclic carbene of the formula II:
  • R 1 , R 2 , R 3 and R 4 are independently selected from C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, C 3-10 cycloalkyl, heteroaryl and aryl, each group being optionally substituted, or R 1 and R 2 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic or polycyclic, saturated or unsaturated ring system that contains 3 to 30 carbon atoms, of which one or more of the carbon atoms is optionally replaced with a heteromoiety selected from O, S, NH and NC 1-6 alkyl, and/or R 3 and R 4 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic or polycyclic, saturated or unsaturated ring system that contains 3 to 30 carbon atoms, of which one or more of the carbon atoms is optionally replaced with a heteromoiety selected from O, S, NH and NC 1-6 alkyl, the
  • R 1 , R 2 , R 3 and R 4 in the ADC's of formula II are independently selected from C 1-6 alkyl, C 5-6 cycloalkyl and aryl, each group being optionally substituted, or R 1 and R 2 and/or R 3 and R 4 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic, saturated ring system that contains 4 to 7 carbon atoms, and the optional substituents on R 1 , R 2 , R 3 and R 4 are independently selected from one or more, optionally one to five, suitably one to three, of C 1-4 alkyl, halo-substituted C 1-4 alkyl, C 5-6 cycloalkyl and aryl, and at least one of R 1 , R 2 , R 3 , R 4 , the ring system formed by R 1 and R 2 and the ring system formed by R 3 and R 4 , or a substituent thereon, comprises at least one chiral center
  • ADC of formula II is selected from:
  • the metal M may be any metal used in catalysts for metal-catalyzed organic synthesis reactions.
  • the metal is any transition metal, or other metal selected from B, Al, Ga, Ge, In, Sn, Sb, Ti, Pb, Bi and Po, or a lanthanide or actinide.
  • suitable metals include, but are not limited to Cu, Ag, Au, Sn, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os and Re.
  • X is selected from any ancillary ligand, including phosphine, amine, alkene, diamine, diphosphine, aminophosphine, halo (for example, fluoro, chloro, bromo or iodo, specifically chloro), HO ⁇ , R 5 O ⁇ and R 5 C(O)O ⁇ , wherein R 5 is H or C 1-6 alkyl.
  • X is chloro.
  • n is greater than 1, it is an embodiment of the disclosure that all X ligands are the same.
  • X may also be a multidentate ligand.
  • n is an integer that will depend on the identity and oxidation state of M and the identity of X.
  • the preparation of the catalysts of formula I is suitably done by generating the ADC ligand in situ from a formamidium salt of formula III, followed by addition of an appropriate metal precursor complex or salt:
  • the ADC of formula II is generated from a formamidium salt of formula III by reaction with a strong base, such as an alkyl lithium or lithium amide, at reduced temperatures, for example at ⁇ 50° C. to about ⁇ 90° C.
  • a strong base such as an alkyl lithium or lithium amide
  • the resulting reaction mixture is then reacted for a time and at a temperature sufficient for the formation of the ADC of formula II (determinable by a person skilled in the art), then the appropriate metal compound is added, suitably at reduced temperatures, for example at ⁇ 50° C. to about ⁇ 90° C., to form the catalysts of formula I.
  • reaction times and temperatures can be varied, depending on the identity of the compounds of formula II and metal precursor compound, to optimize the yield of the catalysts of formula I.
  • the catalysts of formula I, so prepared, may be used without isolation in any organic synthesis transformation.
  • the present disclosure further includes a formamidium salt useful as a precursor to the chiral ADC's of the present disclosure. Accordingly, the present disclosure includes a chiral formamidium salt of the formula III:
  • R 1 , R 2 , R 3 and R 4 are independently selected from C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, C 3-10 cycloalkyl, heteroaryl and aryl, each group being optionally substituted, or R 1 and R 2 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic or polycyclic, saturated or unsaturated ring system that contains 3 to 30 carbon atoms, of which one or more of the carbon atoms is optionally replaced with a heteromoiety selected from O, S, NH and NC 1-6 alkyl, and/or R 3 and R 4 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic or polycyclic, saturated or unsaturated ring system that contains 3 to 30 carbon atoms, of which one or more of the carbon atoms is optionally replaced with a heteromoiety selected from O, S, NH and NC 1-6 alkyl, and
  • R 1 , R 2 , R 3 and R 4 in the formamidium salts of formula III are independently selected from C 1-6 alkyl, C 5-6 cycloalkyl and aryl, each group being optionally substituted, or R 1 and R 2 and/or R 3 and R 4 are linked to form, together with the nitrogen atom to which they are attached, an optionally substituted monocyclic, saturated ring system that contains 4 to 7 carbon atoms, and the optional substituents on R 1 , R 2 , R 3 and R 4 are independently selected from one or more, optionally one to five, suitably one to three, of C 1-4 alkyl, halo-substituted C 1-4 alkyl, C 5-6 cycloalkyl and aryl, and at least one of R 1 , R 2 , R 3 , R 4 , the ring system formed by R 1 and R 2 and the ring system formed by R 3 and R 4 , or a substituent thereon, comprises at least one chiral
  • Y is any non-coordinating counter anion, including, for example, BF 4 ⁇ or B(C 6 F 5 ) 4 .
  • the formamidium salt of formula (III) is selected from:
  • Y is a counteranion
  • analogs of the above compounds that are substituted on the alkyl groups, phenyl rings, aromatic and/or pyrrolidine rings with one or more substituents independently selected from C 1-6 alkyl, halo, halo-substituted C 1-6 alkyl, OC 1-6 alkyl and halo-substituted OC 1-6 alkyl.
  • the formamidium salts of formula III may be prepared, for example, by reacting an aldehyde of formula IV with an amine of the formula V under Vilsmeier Haack reaction conditions, for example in the presence of POCl 3 , or equivalent reagent, at reduced temperatures (e.g. about 10° C. to ⁇ 90° C.) in an inert anhydrous solvent.
  • R 1 , R 2 , R 3 and R 4 are as defined in formula III.
  • the POCl 3 , or equivalent reagent is added to the compound of formula IV at about ⁇ 50° C. to about ⁇ 90° C., followed by warming to room temperature for a time sufficient to form the intermediate iminium salt and the resulting mixture is cooled to about 5° C. to about ⁇ 5° C. and the amine of formula V is added.
  • the reaction times and temperatures can be varied, depending on the identity of the compounds of formula IV and V, to optimize the yield of the compounds of formula III.
  • the compounds of formula IV and V are either commercially available or may be prepared using methods known in the art, for example as described herein below.
  • the present disclosure also includes a method of performing metal-catalyzed organic synthesis reactions comprising contacting substrates for the organic synthesis reaction with a metal catalyst of the formula I as defined above under conditions for performing the organic synthesis reaction, and optionally isolating one or more products from the organic synthesis reaction.
  • the organic synthesis reaction is any reaction the benefits from the presence or use of a metal catalyst, for example, but not limited to, hydrosilations, hydrogenations, conjugate additions and cross-couplings (for example Suzuki, Sonogashira and Heck reactions).
  • the organic synthesis transformation is an asymmetric or chiral synthesis reaction (i.e. provides one enantiomer in excess of the other).
  • the catalyst of formula I is generated in situ in solution and the resulting catalyst solution is added to the appropriate starting materials for the organic synthesis transformation.

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US6888002B2 (en) 2001-10-02 2005-05-03 Bayer Aktiengesellschaft Transition metal complexes with diaminocarbene ligands and their use in reactions catalyzed by transition metals

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